JP5980088B2 - Developer composition for 3D printer modeled object, method for developing 3D printer modeled object, and method for manufacturing 3D printer modeled object - Google Patents

Description

  The present invention relates to a developer composition for a 3D printer model, a method for developing a 3D printer model using the same, and a method for manufacturing a 3D printer model.

  A 3D printer is a type of rapid prototyping (3D modeling machine) that uses 3D data such as 3D CAD and 3D CG created on a computer as a design drawing to create a 3D plastic model (3D object). It is a printer. Specifically, inkjet UV curable 3D printers using acrylic photo-curing resins (eg, CONNEX and EDEN manufactured by Objet Geometry, AGILISTA-3000 manufactured by Keyence), and ABS resins (acrylonitrile, butadiene, styrene, etc.) Resin), polycarbonate resin (PC), polyphenylsulfone resin (PPSF) and the like are known to be 3D printers (for example, FORTUS, Dimension, uPrint, etc., manufactured by Stratasys).

  In modeling with a 3D printer, two types of resin, a model material that is a material of the modeling model itself and a support material that holds the shape, are used, and the shape is made with the model material while supporting the space portion with the support material. For example, in an inkjet ultraviolet curing method using an acrylic photo-curing resin, a three-dimensional object is formed by irradiating a liquid model resin with light such as ultraviolet rays and curing the plastic little by little. Therefore, the modeling model is completed by removing the support material in the space portion. As the model material, an acrylic photo-curing resin or the like is used in the inkjet ultraviolet curing method, and an ABS resin or the like is used in the hot melt lamination method. As the support material, acrylic resin or the like is used for both types.

  3D printers are widespread in a wide range of fields such as architecture, medical care, education, and advanced research, mainly in the manufacturing industry. Before actually making a product, each part is reduced to a size that can be output by a 3D printer, and used for prototypes such as design verification and functional verification. Specifically, in the manufacturing field, as a prototype or mock-up such as “design examination” and “functional verification” of products and parts, in the architectural field as “architectural models” for competitions and presentations, in the medical field, computer tomography and As a "model for preoperative study" based on data such as nuclear magnetic resonance imaging, as a "manufacturing education tool" in the education field, and in the advanced research field, "test parts" It is used for creation purposes such as “Ingredients”.

  As a merit of using a 3D printer, what can only be seen on the screen of a personal computer until now is a model, but you can pick up what was actually completed, so the image when completed is very much It becomes easier. As a result, even when actually produced, a completed image is created, and there is no need to get lost, so work efficiency is improved.

  In order to make a more detailed evaluation, which is the purpose of the 3D printer, it is necessary to reliably remove the support material without damaging a modeling model of a fine part such as a boss or a rib or a thin part.

  As a method for removing the support material, many methods have been used, such as using a metal spatula to remove most of the support material manually and then finishing with a brush. However, not only the support material on the surface could not be completely removed, but also the support material on the inner surface, small holes and grooves, particularly the bag hole-like portion, could not be completely removed. In addition, it may be possible to remove the support material with a solvent or a cleaning agent. However, conventional cleaning agents for resin stains not only support the support material, but also affect the model material. It was hard to say that it showed a good effect.

  Conventionally, with regard to the removal of the support material, a removal device as in Patent Literatures 1 to 3 and a method as in Patent Literatures 3 to 6 have been proposed.

JP 2011-5666 A JP 2011-5667 A JP 2011-5668 A JP 2011-5658 A JP 2011-20212 A JP 2012-192679 A

  However, in the devices of Patent Documents 1 to 3 and the method of Patent Document 6, the surface support material can be removed relatively completely, but the inner surface, small holes, grooves, especially the support material in the bag hole-shaped part, It was found that it could not be completely removed. In addition, weak parts such as fine parts and thin parts of the model material may be destroyed. On the other hand, it has also been found that the methods of Patent Documents 4 and 5 cannot sufficiently remove the support material.

  The present invention does not affect the model material of the 3D printer model, and the developer composition for the 3D printer model that enables the support material to be removed well, the method for developing the 3D printer model using the same, and A method for producing a 3D printer model is provided.

  The present invention relates to (a) a water-soluble organic solvent (hereinafter referred to as component (a)) of 1% by weight or more and 20% by weight or less, (b) an alkali metal hydroxide (hereinafter referred to as component (b)) 0.5 % By weight or more and 20% by weight or less, (c) organic alkali agent (hereinafter referred to as component (c)) 0.2% by weight or more and 20% by weight or less, (d) surfactant (hereinafter referred to as component (d)) ] 0.1 wt% or more, 20 wt% or less, and water, and the weight ratio (b) / (c) of the content of (b) to the content of (c) is 1/4 or more, 1 / The present invention relates to a developer composition for a 3D printer shaped article that is 0.4 or less.

The present invention also provides:
The development process of removing the support material by processing the 3D printer modeled object modeled with the model material and the support material with the developer composition for 3D printer modeled object, and the 3D printer modeled object after the development process with water or water A method for developing a 3D printer model, including a rinsing process for processing with a liquid containing
The developer composition for a 3D printer object is (a) a water-soluble organic solvent of 1% by weight to 20% by weight, (b) an alkali metal hydroxide of 0.5% by weight to 20% by weight, ( c) an organic alkali agent of 0.2 wt% or more and 20 wt% or less, (d) a surfactant of 0.1 wt% or more and 20 wt% or less, and water, and the content of (b) and (c ) Content weight ratio (b) / (c) is a developer composition for a 3D printer modeled article of 1/4 or more and 1 / 0.4 or less,
The present invention relates to a method for developing a 3D printer model.

The present invention also provides:
3D modeling process for manufacturing a D printer modeled object composed of a model material and a support material using a 3D printer,
A development process for removing the support material from the 3D printer model by processing the 3D printer model obtained in the 3D model process with a developer composition for a 3D printer model, and a 3D printer model after the development process. A method for producing a 3D printer shaped article, comprising a rinsing process for treating with water or a liquid containing water,
The developer composition for a 3D printer object is (a) a water-soluble organic solvent of 1% by weight to 20% by weight, (b) an alkali metal hydroxide of 0.5% by weight to 20% by weight, ( c) an organic alkali agent of 0.2 wt% or more and 20 wt% or less, (d) a surfactant of 0.1 wt% or more and 20 wt% or less, and water, and the content of (b) and (c ) Content weight ratio (b) / (c) is a developer composition for a 3D printer modeled article of 1/4 or more and 1 / 0.4 or less,
The present invention relates to a method for manufacturing a 3D printer model.

  According to the present invention, there is no influence on the model material of the 3D printer model, and the developer composition for the 3D printer model that allows the support material to be removed satisfactorily, and the development method of the 3D printer model using the same, And the manufacturing method of 3D printer modeling thing can be provided.

Model figure which shows the outline of the test piece (3D printer modeling thing) which was modeled with the example and comparative example

<Developer Composition for 3D Printer Model>
The developer composition for a 3D printer shaped article of the present invention (hereinafter sometimes abbreviated as “developer composition”) includes a specific water-soluble organic solvent, an alkali metal hydroxide, an organic alkali agent, and a surface activity. By containing the agent and water, the model material of the 3D printer model is not affected, and the support material can be removed satisfactorily.

[(A) component: water-soluble organic solvent]
The water-soluble organic solvent (a) exhibits the performance of swelling of the support material, penetration of the developer composition into the resin, collapse of the support material, and dissolution in the developer composition.

  The water-soluble organic solvent is preferably one that dissolves 1.5% by weight or more in water at 20 ° C. Examples of the water-soluble organic solvent include water-soluble organic solvents selected from monohydric alcohols, polyhydric alcohols, and glycol ethers.

  Examples of the monohydric alcohol include monohydric alcohols having 1 to 5 carbon atoms. Specifically, a monohydric alcohol selected from methyl alcohol, ethyl alcohol, 1-propyl alcohol, isopropyl alcohol, allyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol, and amyl alcohol Can be mentioned.

  Examples of the polyhydric alcohol include alkylene glycols having a repeating unit having 2 to 3 carbon atoms (hereinafter referred to as C2-C3 alkylene glycol). As C2-C3 alkylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, propylene glycol, dipropylene Examples include glycol and tripropylene glycol. The C2-C3 alkylene glycol preferably has 1 to 10 oxyethylene groups or oxypropylene groups which are repeating units.

  Examples of the polyhydric alcohol other than C2 to C3 alkylene glycol include polyhydric alcohols having 2 to 8 carbon atoms. Specifically, trimethylene glycol, 1,3-octylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-pentanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, glycerin, Examples include trimethylolethane and trimethylolpropane.

  Examples of the glycol ether include glycol ethers selected from polyoxyalkylene monoalkyl ethers and polyoxyalkylene dialkyl ethers. These oxyalkylene groups are preferably oxyethylene groups. Moreover, the average added mole number of the oxyalkylene group is preferably 1 or more and 7 or less. The number of carbon atoms in the alkyl group (the alkyl group in the terminal ether portion) is preferably 1 or more and 4 or less. Specifically, PEO (1 to 7) monomethyl ether, PEO (1 to 7) monoethyl ether, PEO (1 to 7) monopropyl ether, PEO (1 to 7) monobutyl ether , PEO (1 or more, 7 or less) monoisobutyl ether, PEO (1 or more, 7 or less) monoallyl ether, PEO (1 or more, 7 or less) monohexyl ether, PEO (1 or more, 7 or less) dimethyl ether, PEO (1 As mentioned above, 7 or less) diethyl ether, PEO (1 or more, 7 or less) dipropyl ether, PEO (1 or more, 7 or less) dibutyl ether, etc. are mentioned. Here, POE is an abbreviation for polyoxyethylene, and the numbers in parentheses are the average added moles of ethylene oxide (the same applies hereinafter).

  The component (a) may be used alone or in combination of two or more. Among these, from the viewpoint of further enhancing the swelling of the support material and the penetration of the developer composition into the resin, the collapse of the support material and the dissolution in the developer composition, methyl alcohol, ethyl alcohol, 1-propyl alcohol, isopropyl Alcohol, t-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, POE (1 or more, 5 or less) monomethyl ether, POE (1 or more, 5 or less) monoethyl ether, POE (1 or more, 5 or less) monopropyl ether, POE (1 or more, 5 or less) monobutyl ether, POE (1 or more, 5 or less) monoisobutyl ether, POE (2 or more, 5 or less) dimethyl ether, and POE (2 or more) 5 or less) A water-soluble organic solvent selected from ethyl ether is preferable. Ethyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, POE (1 or more, 3 or less) monomethyl ether, POE (1 or more, 3 or less) A water-soluble organic solvent selected from monoethyl ether, POE (1 to 3) monopropyl ether, POE (1 to 3) monobutyl ether, and POE (1 to 3) monoisobutyl ether is more preferable.

  The content of the water-soluble organic solvent as component (a) is determined from the viewpoint of further enhancing the swelling of the support material and the penetration of the developer composition into the resin, the collapse of the support material and the dissolution in the developer composition. In the product, it is 1% by weight or more and 20% by weight or less. From the viewpoint of enabling the support material to be removed satisfactorily, safety during handling, and economical efficiency, the content of the component (a) is 3% by weight or more, further 5% by weight or more, and further 7% in the composition. It is preferably 15% by weight or more, more preferably 12% by weight or less, and further preferably 10% by weight or less.

[(B) component: alkali metal hydroxide]
The alkali metal hydroxide as the component (b) exhibits saponification, decomposition, disintegration, and dissolution performance in the developer composition of the support material.

  Examples of the alkali metal hydroxide include an alkali metal hydroxide selected from lithium hydroxide, sodium hydroxide, and potassium hydroxide. (B) A component may be used independently, respectively, but 2 or more types may be used together. Among these, an alkali metal hydroxide selected from sodium hydroxide and potassium hydroxide is preferable from the viewpoint of further enhancing saponification, decomposition, disintegration and dissolution of the support material in the developer composition.

  The content of the alkali metal hydroxide as component (b) is 0 in the composition from the viewpoint of achieving both good removal of the support material and no influence on the model material of the 3D printer model. 0.5 wt% or more and 20 wt% or less. From the viewpoint of further enhancing saponification, decomposition, disintegration and dissolution in the developer composition of the support material, and from the viewpoint of safety during handling, the content of the component (b) is 1% by weight or more in the composition, Further, 2% by weight or more, further 3% by weight or more is preferable, and 15% by weight or less, further 10% by weight or less, and further 5% by weight are preferable.

[(C) component: organic alkali agent]
The organic alkali agent of component (c) is the same as the water-soluble organic solvent of component (a), and the swelling of the support material and the penetration of the developer composition into the resin, the collapse of the support material and the developer composition. In addition to exhibiting the performance of dissolution, the combination of (b) alkali metal hydroxide reduces the influence on the model material of the 3D printer model and exhibits the performance of achieving both good removal of the support material.

  An amine compound is mentioned as an organic alkali agent. Further, examples include amine compounds having 1 to 5, 5 or less primary, secondary and / or tertiary amine nitrogen atoms in one molecule and having a molecular weight of 50 to 300.

  Examples of the amine compound include compounds described in JP-A No. 8-157878, paragraphs 0019 to 0028 (page 4, column 5, line 32 to page 5, column 7, line 7).

  Specifically, an alkanolamine, a monoamine, a diamine which may have a substituent, a triamine which may have a substituent, a morpholine which may have a substituent, and a substituent. And an amine compound selected from pyridine, which may have a substituent, and piperidine which may have a substituent, and tetraamine which may have a substituent.

  These may be used alone or in combination of two or more. Among these, from the viewpoint of developability and rinsing properties, monoethanolamine, diethanolamine, triethanolamine, methylmonoethanolamine, dimethylmonoethanolamine, methyldiethanolamine, butylmonoethanolamine, trimethylaminopropylethanolamine, N-amino Alkanolamines such as ethylethanolamine; diaminopropane, diaminohexane, diaminooctane, diaminododecane, 4,4′-methylenebis (cyclohexylamine), 1,3-diaminoxylene, 1,3-bis (aminomethyl) cyclohexane, tri Ethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, methyldiaminopropane, dimethyldiame Diamines such as propane, dibutyldiaminopropane, N-cyclohexyl-1,3-diaminopropane; monomethylamine, monoethylamine, monopropylamine, monobutylamine, monoamylamine, monohexylamine, monooctylamine, monodecylamine, mono Linear alkyl groups or branches such as laurylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, methylethylamine, methylpropylamine, methylbutylamine, methylhexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine Monoamine having a chain alkyl group; morpholine, N-methylmorpholine, N-ethylmorpholine, 2,6-dimethylmorpholine, 4- (2-hydride) Morpholine optionally having substituents such as xylethyl) morpholine, 4-aminomorpholine, 4- (2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine; Examples include pyridine; piperidine which may have a substituent; triamine which may have a substituent; tetraamine which may have a substituent.

  Furthermore, from the viewpoints of safety in handling and easy availability, it may have an alkanolamine, a diamine, a monoamine having a linear alkyl group (preferably having a carbon number of 1 or more and 12 or less), and a substituent. An amine compound selected from morpholine is preferred.

  The content of the organic alkali agent as component (c) is determined by the effects of swelling of the support material and penetration of the developer composition into the resin, disintegration of the support material and dissolution in the developer composition, and In combination with alkali metal hydroxide, 0.2% by weight or more in the composition from the viewpoint of reducing the influence on the model material of the 3D printer model and achieving good removal of the support material. 20% by weight or less. From the viewpoint of preventing the corrosion of the model material surface by the organic alkali agent and the effect of the combination of the component (b) with the alkali metal hydroxide, the content of the component (c) is 0.5% by weight or more in the composition. Further, 1% by weight or more, further 2% by weight or more is preferable, and 15% by weight or less, further 10% by weight or less, and further 5% by weight or less are preferable.

  The total content of the component (b) and the component (c) is preferably 1.5% by weight or more, more preferably 3% by weight or more, and further 5% by weight in the composition, and 30% by weight or less, further 20% by weight. % Or less, more preferably 10% by weight or less.

  In the present invention, the weight ratio (b) / (c) of the content of the component (b) to the content of the component (c) is not less than 1/4 and not more than 1/4. When the weight ratio (b) / (c) is 1/4 or more, the effects of saponification, decomposition, and collapse of the support material by the alkali metal hydroxide as the component (b) are sufficiently exhibited. Also, the dispersion stability of pigments and the like that can be arbitrarily blended is improved. Moreover, if this weight ratio is 1 / 0.4 or less, the influence on the model material of the alkali metal hydroxide of (b) component can be reduced. 1 / 0.5 or less from the viewpoint of the effect of reducing the influence on the model material of the 3D printer modeled object by combining the organic alkali agent and the alkali metal hydroxide, and achieving both good removal of the support material. It is preferably 1 / 0.6 or less, more preferably 1 / 0.7 or less, and more preferably 1/3 or more, further 1/2 or more, and further preferably 1/1 or more.

  In the present invention, the combined use of the component (b) and the component (c) and using them at a predetermined weight ratio does not affect the model material of the 3D printer model, and allows the support material to be removed satisfactorily. It is one of the factors contributing to the manifestation of the effects of the invention. As described above, the component (b) contributes to saponification, decomposition, and disintegration of the support material and dissolution of the support material in the developer composition. On the other hand, the component (c) is also a component that contributes to removal of the support material due to swelling of the support material. In the present invention, the reason why the support material can be sufficiently removed by the component (b) and the component (c) and the surface condition of the model material can be improved is not necessarily clear, but the component (b) and the component (c) When the weight ratio of the components is within the predetermined range, the component (c) is likely to be present on the surface of the model material, and the influence of the component (b) on the model material can be reduced, so the surface state of the model material is improved. It is presumed to be preserved.

[(D) component: surfactant]
The surfactant as component (d) exhibits stabilization of the developer composition, permeability into the resin, and high rinsing performance.

  Examples of the surfactant include a surfactant selected from an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Specific examples of the surfactant include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, aliphatic amines, aliphatic amide sulfates, fatty alcohol phosphates, dibasic fatty acid esters. Anionic surfactants such as sulfonate, fatty acid amide sulfonate, alkyl allyl sulfonate, and naphthalene sulfonate of formalin condensation; polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl amine , Polyoxyalkylene alkyl esters, sorbitan alkyl esters, polyoxyalkylene sorbitan alkyl esters and other nonionic surfactants; alkylbetaines, alkyldimethylamine oxides, alkylalanines and the like Sex surfactants.

  The component (d) may be used alone or in combination of two or more. Among these, from the viewpoint of stabilization of the developer composition, penetration into the resin, and high rinsing performance, anionic surfactants include alkylbenzene sulfonate, alkyl sulfate ester salt, alkyl ethoxy sulfate ester salt, and olefin. Anionic interfaces selected from sulfonates, alkanesulfonates, fatty acid salts, alkyl ethoxycarboxylates, α-sulfo fatty acid salts, α-sulfo fatty acid ester salts, alkenyl succinates, and fatty alcohol phosphate ester salts An activator is preferred. From the same viewpoint, nonionic surfactants include ethylene oxide / propylene oxide block polymers, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides, polyoxypropylene alkyl ethers, sucrose fatty acids. Nonionic surfactants selected from esters and tertiary amine oxides are preferred. From the same viewpoint, the amphoteric surfactant is preferably an amphoteric surfactant selected from betaine and sulfobetaine. Furthermore, from the viewpoint of easy availability, an anionic surfactant is preferably an alkylbenzene sulfonic acid, and a nonionic surfactant is preferably a polyoxyethylene alkyl ether.

  The content of the surfactant as the component (d) is 0.1% by weight or more and 20% by weight or less in the composition from the viewpoint of stabilization of the developer composition, penetration into the resin, and high rinsing. is there. From the viewpoint of stabilization of the developer composition and economy, the content of the component (d) is preferably 0.3% by weight or more, more preferably 0.5% by weight or more, and further preferably 1% by weight or more in the composition. And 10 weight% or less, 5 weight% or less, Furthermore 3 weight% or less are preferable.

〔water〕
The developer composition of the present invention contains water. Examples of water include ultrapure water, pure water, ion exchange water, distilled water, and normal tap water. The content of water may be the balance of the composition (a total amount of 100% by weight). From the viewpoint of improving the stability and handleability of the developer composition and considering the environment by improving the waste liquid processability and the like, the water content is 20% by weight or more, and further 45%. % By weight or more, further 63% by weight or more, more preferably 77% by weight or more, and 98.2% by weight or less, further 95.2% by weight or less, further 91.5% by weight or less, and further preferably 87% by weight or less. .

[Optional ingredients]
In the developer composition of the present invention, builder components such as ethylenediaminetetraacetate, carboxymethylcellulose, polyvinylpyrrolidone, polyacrylate, alginate, and the like are added as necessary, as long as the effects of the present invention are not impaired. Agents, pH adjusters, antiseptics, rust inhibitors, pigments, colorants, fragrances, bactericides, and the like may be included. Depending on the type of the support material, the developer composition containing the colorant changes color when the support material dissolves. Therefore, the colorant is also expected to function as an indicator that indicates the degree of progress and completion of development. it can.

  The developer composition of the present invention can be prepared by mixing the component (a), the component (b), the component (c), and the component (d), water, and optional components used as necessary. .

[Model materials and support materials]
The developer composition of the present invention is preferably a 3D printer model using a support material selected from a photocurable composition containing an acrylic monomer and a thermoplastic acrylic resin as a support material. Specifically, the developer composition of the present invention is an inkjet ultraviolet curable system using a photocurable composition containing an acrylic monomer as a model material and a support material, or ABS resin, polycarbonate, polysiloxane as a model agent. It is preferable to use a 3D printer modeled by a 3D printer modeled by a hot melt lamination method using a thermoplastic resin such as phenyl sulfone and using a thermoplastic acrylic resin as a support material. And the developing solution composition of this invention is used in order to remove a support material from this 3D printer modeling thing. Therefore, the developer composition of the present invention can dissolve the support material but does not dissolve the model material.

  The support material targeted by the developer composition of the present invention is preferably a support material selected from a photocurable composition containing an acrylic monomer and a thermoplastic acrylic resin. Examples of the photocurable composition include a liquid composition containing a photopolymerizable acrylic monomer, a water-soluble viscosity modifier, a wetting agent, and a photopolymerization initiator. Specifically, photopolymerizable acrylic monomers, water-soluble viscosity modifiers such as polyethylene glycol and polyhydric alcohols, wetting agents such as glycerin (which may function as a water-soluble viscosity modifier), photopolymerization initiators, etc. The liquid composition containing is mentioned.

  Examples of the acrylic monomer used for the support material include photopolymerizable acrylic monomers. Examples of the acrylic monomer, preferably a photopolymerizable acrylic monomer, include non-functional acrylic monomers, monofunctional acrylic monomers, and polyfunctional acrylic monomers. The acrylic monomer used for the support material is a monomer that becomes an acrylic resin.

  Non-functional acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate, Lauryl acrylate, tridecyl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, Methacrylic acid cyclohexyl, benzyl methacrylate.

  Further, as monofunctional acrylic monomers, acrylic acid, diethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, methacrylic acid, diethylaminoethyl methacrylate, Examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate.

  Polyfunctional acrylic monomers include ethylene diacrylate, diethylene glycol diacrylate, 1,3-butylene diacrylate, triethylene glycol diacrylate, allyl acrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, and diacryl. Decaethylene glycol acid, pentaerythritol tetraacrylate, pentadecaethylene glycol diacrylate, ethylene dimethacrylate, diethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, triethylene glycol dimethacrylate, allyl methacrylate, dimethacrylate Tetraethylene glycol acid, trimethylolpropane trimethacrylate, decaethylene glycol dimethacrylate, pentamethacrylate Suritoru include pentadecafluorooctyl glycol dimethacrylate.

  As acrylic monomers, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, methacrylic acid, 2-hydroxyethyl methacrylate, An acrylic monomer selected from ethylene diacrylate, 1,3-butylene diacrylate, ethylene dimethacrylate, and 1,3-butylene dimethacrylate is preferred.

Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators.
Specific examples of radical photopolymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- ( 2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone and other alkylphenone photoinitiators; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -sulfur Acylphosphine oxide photopolymerization initiators such as nylphosphine oxide; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) ) -Phenyl) titanium and other titanocene photoinitiators: other 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
Specific examples of the cationic photopolymerization initiator include iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-), and the like.

  As a liquid composition for a support material targeted by the developer composition of the present invention, as a photocurable composition containing an acrylic monomer, an acrylic monomer is 20% by weight or more, 50% by weight or more, polyethylene glycol 30 wt% or more and 75 wt% or less of a water-soluble viscosity modifier such as polyhydric alcohol, and 5 wt% or more and 20 wt% or less of a wetting agent such as glycerin (which may function as a water-soluble viscosity modifier). And a liquid composition containing 1% by weight or more of a photopolymerization initiator.

  As a model material targeted by the developer composition of the present invention, a photocurable composition containing an inkjet ultraviolet curable acrylic monomer, an acrylic oligomer, a photopolymerization initiator, or the like (that is, an ultraviolet curable composition). And a thermoplastic resin such as a hot melt laminated ABS resin, polycarbonate, and polyphenylsulfone. As the acrylic monomer used in the ink jet ultraviolet curing model agent, those exemplified for the support material can be used. The difference between the model material and the support material is that the model material does not contain a water-soluble viscosity modifier and a wetting agent, contains an acrylic oligomer, and the degree of polymerization of the 3D modeled object is high.

  The developer composition of the present invention uses (i) a model material composed of a photocurable composition containing an acrylic monomer, an acrylic oligomer, a photopolymerization initiator, etc. A support material using a thermoplastic tree such as ABS resin, polycarbonate, polyphenylsulfone, etc. as a model material using a cured acrylic resin, preferably a 3D printer by an inkjet ultraviolet curing 3D printer, and (ii) a model material As a 3D printer model using a thermoplastic acrylic resin, preferably a 3D printer model using a hot melt lamination type 3D printer, it can be suitably used.

  In addition, in this specification, among the matters described in the following sections of the development method of the 3D printer modeled object and the method of manufacturing the 3D printer modeled object of the present invention, the applicable ones are those for developing the 3D printer modeled object of the present invention. It can be incorporated into the liquid composition.

<Development Method for 3D Printer Model>
A method for developing a 3D printer model using the developer composition of the present invention will be described.

The developing method of the 3D printer shaped object of the present invention is as follows:
A development process for removing a support material by processing a 3D printer modeled object modeled with a model material and a support material with the developer composition for 3D printer modeled article of the present invention, and a 3D printer modeled object after the development process, A rinsing process for treating with water or a liquid containing water is included.

(Development process)
In the development step, the 3D printer modeled object modeled with the model material and the support material is treated with the developer composition for 3D printer modeled article of the present invention to remove the support material. It is preferable to remove the support material to such an extent that the support material cannot be visually confirmed on the surface of the model material. Further, it is desired that the developing process be performed without dissolving the model material as much as possible. The developer composition used in the development step is preferably colored. Examples of the color to be colored include blue and green. Moreover, it is preferable that it is a color which a developer composition discolors by melt | dissolution of a support material.

  The 3D printer is preferably a 3D printer that uses a movable nozzle with a built-in inkjet nozzle or heater. A 3D printer that uses inkjet nozzles is a so-called inkjet 3D printer. As the model material and the support material used for modeling the 3D printer modeled object, those described in the section of the developer composition for the 3D printer modeled object of the present invention in this specification can be used, respectively. is there. In the method for developing a 3D printer model according to the present invention, the model material is preferably made of a photocurable composition containing an acrylic monomer, and the support material is preferably made of a photocurable composition containing an acrylic monomer. In this case, the 3D printer is preferably a 3D printer that uses inkjet nozzles. In the method for developing a 3D printer model according to the present invention, it is also preferable that the model material is made of a thermoplastic tree and the support material is made of a thermoplastic acrylic resin. In this case, the 3D printer is movable with a built-in heater. A 3D printer using nozzles is preferred.

  The treatment with the developer composition of the present invention in the development step is performed by bringing the composition into contact with the 3D printer model, and a method of immersing the 3D printer model in the composition is preferable. For example, immersion method (immerse and leave still), immersion rocking method (rocking under immersion), immersion stirring method (stirring under immersion), immersion bubbling method (bubbling during immersion), in liquid Examples include a jet method and an immersion ultrasonic cleaning method. The immersion method is preferable from the viewpoint that no special apparatus is required. Immersion is performed so that the entire 3D printer model is in contact with the developer composition of the present invention. That is, the entire 3D printer model is immersed in the developer composition of the present invention.

  The temperature of the developer composition at the time of performing the treatment with the developer composition may be appropriately adjusted according to the support material adhesion amount, etc., for example, improvement of developability, support material removability and moisture evaporation From the viewpoint of reducing the effect on the model material, 5 ° C. or higher, further 10 ° C. or higher, further 20 ° C. or higher is preferable, and 60 ° C. or lower, further 50 ° C. or lower, and further 40 ° C. or lower is preferable. When the model material is an ultraviolet curable resin, the temperature of the developer composition for a 3D printer shaped article used in the development process is preferably 5 ° C. or higher and 40 ° C. or lower.

  The development time is appropriately adjusted according to the remaining amount of the support material. In the case of the dipping method, the dipping time is preferably 1 hour or longer, more preferably 2 hours or longer, and further preferably 3 hours or longer, and preferably 24 hours or shorter, further 12 hours or shorter, and further 6 hours or shorter.

(Rinsing process)
In the rinsing process, the 3D printer model after the development process is processed with water or a liquid containing water. The treatment with water or a liquid containing water is performed by bringing water or a liquid containing water into contact with the 3D printer model after the development process. For the treatment with an aqueous acid solution, a known rinsing method that is usually used can be used. For example, various rinsing treatments such as jetting of flowing water (flowing water rinsing), immersion method, ultrasonic cleaning method, immersion ultrasonic cleaning method, and immersion rocking method can be used alone or in combination.

In the developing method of the 3D printer shaped article of the present invention, the rinsing process is
A first rinsing process for treating the 3D printer model after the development process with an aqueous solution of an acid, and a second rinsing process for treating the 3D printer model after the first rinsing process with water,
It is preferable to contain. Hereinafter, the first rinsing process and the second rinsing process will be described.

(First rinsing process)
In the first rinsing process, the 3D printer model after the development process is treated with an aqueous acid solution. The aqueous solution of the acid used in the first rinsing treatment step can be obtained, for example, by dissolving the following water-soluble acid in water.

  The water-soluble acid may be either an inorganic acid or an organic acid, or both. Inorganic acids are preferred from the standpoint of strong acidity and high ability to remove developer components. From the viewpoint of good handling safety and rinsing properties, organic acids are preferred.

  Examples of the inorganic acid include oxo acid, peroxo acid, and hydrogen acid. Examples of oxo acids include boric acid, iodic acid, nitric acid, phosphoric acid, sulfuric acid, hypochlorous acid, perchloric acid, nitrous acid, hypophosphorous acid, phosphorous acid, and sulfurous acid. Examples of peroxo acids include persulfuric acid, percarbonate, perphosphoric acid, peracetic acid, perbenzoic acid, and the like. Examples of hydroacid include hydrobromic acid, hydrochloric acid, hydroiodic acid, hydrosulfuric acid and the like. These may be used alone or in combination of two or more. Among these, nitric acid, phosphoric acid, sulfuric acid, or hydrochloric acid, which has a high ability to remove residual developer components and has good durability as an acid, is preferable.

  Examples of the organic acid include water-soluble organic acids such as carboxylic acid, thiocarboxylic acid, peracid, mercaptan, sulfonic acid, phosphatidic acid, dithiocarboxylic acid, sulfinic acid, phosphonic acid, and phosphinic acid.

  Specific examples of the organic acid include linear saturated monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, and propionic acid; linear unsaturated monocarboxylic acids such as acrylic acid, crotonic acid, and vinyl acetic acid; Branched saturated monocarboxylic acids such as isobutyric acid, isovaleric acid and pivalic acid; Branched unsaturated monocarboxylic acids such as methacrylic acid and tiglic acid; Saturated polyvalent carboxylic acids such as oxalic acid, malonic acid, succinic acid and glutaric acid; Unsaturated polyvalent carboxylic acids such as acid and citraconic acid; hydroxycarboxylic acids such as lactic acid, gluconic acid, tartaric acid, malic acid and citric acid; alicyclic carboxylic acids such as cyclohexanecarboxylic acid; polyacrylic acid and polymaleic acid Saturated polycarboxylic acid; thiocarboxylic acid such as o-thioacetic acid; peracid such as peracetic acid; benzenesulfonic acid, toluenesulfonic acid, naphthalene Sulfonic acid, and the like; naphthol sulfonic acids; taurine, naphthylamine sulfonic acid; sulfonic acids such as sulfobenzoic acid, dithiocarboxylic acid, sulfinic acid, phosphonic acid and phosphinic acid. These may be used alone or in combination of two or more.

  Among them, formic acid, formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, which have high ability to remove residual developer components and have good acid durability Acid, citraconic acid, lactic acid, gluconic acid, tartaric acid, malic acid, citric acid, polyacrylic acid and polymaleic acid are more preferred.

  The acid content contained in the acid aqueous solution used in the first rinsing treatment step is preferably 0.1% by weight or more in order to remove the developer composition on the surface of the 3D printer model. The upper limit of the acid content is preferably as high as possible from the viewpoint of removing the developer composition. However, since it is difficult to adjust an acid aqueous solution having a concentration exceeding 98% by weight, the upper limit of the acid content contained in the acid aqueous solution used in the first rinsing treatment may be 98% by weight or less.

  When the acid is an inorganic acid, the content of the inorganic acid in the aqueous solution of the acid increases the removability of the developer composition and the support material dissolved in the developer composition, and improves the sustainability. From the viewpoint, 0.2% by weight or more, further 1% by weight or more, further 5% by weight or more is preferable, and 20% by weight or less, further 15% by weight or less, and further 10% by weight or less are preferable.

  When the acid is an organic acid, the content of the organic acid in the aqueous solution of the acid is uniformly dissolved in water from the viewpoint of enhancing the removability of the developer composition and the support material dissolved in the developer composition and improving the sustainability. In view of the above, 1% by weight or more, further 5% by weight or more, further 10% by weight or more is preferable, and 50% by weight or less, further 30% by weight or less, and further 20% by weight or less are preferable.

  As the water used for the aqueous acid solution used in the first rinsing process, ultrapure water, pure water, ion exchange water, distilled water, ordinary tap water, or the like is used.

  The treatment with the acid aqueous solution in the first rinsing treatment step is performed by bringing the acid aqueous solution into contact with the 3D printer model after the development step. For the treatment with an aqueous acid solution, a known rinsing method that is usually used can be used. For example, various rinsing processes such as an immersion method, an ultrasonic cleaning method, an immersion ultrasonic cleaning method, and an immersion rocking method can be used alone or in combination. The treatment with the acid aqueous solution in the first rinsing treatment step is preferably performed by immersing the 3D printer model after the development step in the acid aqueous solution. Immersion is performed so that the entire 3D printer model after the development process comes into contact with an aqueous acid solution. That is, the entire 3D printer model after the development process is immersed in an acid aqueous solution.

  The temperature of the acid aqueous solution at the time of the treatment with the acid aqueous solution may be appropriately adjusted according to the amount of the support material attached. For example, the development property, the support material removal property improvement, and the water evaporation amount are reduced. From the viewpoint of reducing the influence on the model material, 5 ° C. or higher, further 10 ° C. or higher, further 20 ° C. or higher is preferable, and 60 ° C. or lower, further 50 ° C. or lower, and further 40 ° C. or lower is preferable. When the model material is an ultraviolet curable resin, the temperature of the aqueous acid solution used in the first rinsing process is preferably 5 ° C. or higher and 40 ° C. or lower.

  The processing time in the first rinsing process is appropriately adjusted according to the remaining amount of support material. In the case of the immersion method, the immersion time is preferably 1 minute or longer, more preferably 5 minutes or longer, further 8 minutes or longer, and further preferably 10 minutes or longer, and preferably 60 minutes or shorter, further 30 minutes or shorter, and further 20 minutes or shorter.

(Second rinsing process)
In the second rinsing process, the 3D printer model after the first rinsing process is treated with water. From the viewpoint of ease of rinsing, tap water, ion-exchanged water, pure water or the like is preferable.

  The treatment with water in the second rinsing process is performed by bringing water into contact with the 3D printer model after the first rinsing process. For the treatment with water, a well-known rinsing treatment method that is usually used can be used. For example, various rinsing treatments such as an immersion method, an immersion ultrasonic cleaning method, an immersion rocking method, a spray method, a flowing water method, and a hand wiping method can be used alone or in combination. The treatment with water in the second rinsing process is preferably performed by rinsing with running water in which the running water is brought into contact with the 3D printer model after the first rinsing process.

  The temperature of the water during the treatment with water may be adjusted as appropriate according to the amount of support material attached, etc., for example, developability, improvement of support material removability, reduction of water evaporation, From the viewpoint of reducing the influence of the above, 5 ° C. or more, further 10 ° C. or more, more preferably 20 ° C. or more is preferable, and 60 ° C. or less, further 50 ° C. or less, and further 40 ° C. or less is preferable. When the model material is an ultraviolet curable resin, the temperature of water used in the second rinsing process is preferably 5 ° C. or higher and 40 ° C. or lower.

  The processing time in the second rinsing process is appropriately adjusted according to the remaining amount of support material. In the case of rinsing with running water, the rinsing time is preferably 1 minute or more, 5 minutes or more, more preferably 10 minutes or more, and further preferably 15 minutes or more, and preferably 60 minutes or less, further 40 minutes or less, and further 20 minutes or less.

<Method for manufacturing 3D printer model>
Moreover, the process by the developing solution composition for 3D printer modeling objects of this invention can also be taken in to the manufacturing method of 3D printer modeling objects.

The manufacturing method of the 3D printer shaped article of the present invention is as follows:
3D modeling process for manufacturing a D printer modeled object composed of a model material and a support material using a 3D printer,
A development process for removing the support material from the 3D printer model by processing the 3D printer model obtained in the 3D model process with the developer composition for a 3D printer model of the present invention, and a 3D printer after the development process It includes a rinsing process for treating the model with water or a liquid containing water.

  What is necessary is just to perform the 3D modeling process which manufactures D printer modeling object which consists of a model material and a support material using a 3D printer according to manufacture of a well-known 3D printer modeling object.

  It is preferable to use an inkjet 3D printer for modeling by an inkjet ultraviolet curing 3D printer. The modeling by the inkjet 3D printer is preferably performed by a so-called optical modeling method. For example, a photocurable composition containing a photopolymerizable monomer serving as a model material and a support material is ejected from an inkjet nozzle, respectively, and is deposited. And a method of curing by irradiating with ultraviolet rays or the like in a predetermined pattern. In stereolithography, the model material and the support material are set to have different degrees of curing. As the model material and the support material used in the 3D modeling process, those described in the section of the developer composition for a 3D printer modeled product of the present invention in the present specification can be used, respectively, and preferable modes are also the same.

  For modeling by a hot melt lamination type 3D printer, it is preferable to use a 3D printer having a movable nozzle with a built-in heater. Modeling with a movable nozzle 3D printer is preferably performed by a method of melting and discharging a so-called thermoplastic resin. For example, a thermoplastic resin as a model material and a support material is melted with a heater, and each is ejected and accumulated from the movable nozzle. Examples of the method include forming a layer and curing a predetermined pattern. In this method, the types of resin of the model material and the support material are different. As the model material and the support material used in the 3D modeling process by the hot melt lamination type 3D printer, those described in the section of the developer composition for a 3D printer modeled product of the present invention in this specification can be used, respectively. Is the same.

  The 3D printer model obtained in the 3D model process is subjected to a predetermined developing process and a predetermined rinsing process using the developer composition for a 3D printer model of the present invention. Also in the method for manufacturing a 3D printer model according to the present invention, the rinsing process includes a first rinsing process for processing the 3D printer model after the development process with an aqueous acid solution, and a 3D printer modeling of the first rinsing process. It is preferable to include the 2nd rinse process process which processes a thing with water. The development step, the first rinse treatment step, and the second rinse treatment step are each performed in the same manner as the method described in the specification of the 3D printer modeled object development method of the present invention in this specification. In addition, all the matters described in the developing method of the 3D printer modeled object can be applied to this manufacturing method, and preferable aspects are also the same.

<Other aspects of the present invention>
The present invention comprises (a) 1% by weight or more and 20% by weight or less of a water-soluble organic solvent, (b) 0.5% by weight or more and 20% by weight or less of an alkali metal hydroxide, (c) an organic alkali agent 0.2 % By weight or more, 20% by weight or less, (d) a surfactant containing 0.1% by weight or more and 20% by weight or less, and water, and the weight ratio of the content of (b) to the content of (c) ( There is also provided a support material remover composition for 3D printer shaped articles, wherein b) / (c) is ¼ or more and 1 / 0.4 or less. In this specification, all the matters described in the section of the developer composition of the present invention of the present invention can be applied to the support material remover composition for 3D printer shaped objects, and preferred embodiments are also the same.

The present invention also includes a step (1) of removing the support material by immersing the 3D printer modeled object modeled by the model material and the support material in the developer composition for 3D printer modeled object of the present invention,
A step (2) of immersing the 3D printer model after step (1) in an acid aqueous solution; and a step (3) of treating the 3D printer model after step (2) with water,
A method for removing a support material of a 3D printer shaped object is also provided. In the present specification, all the matters described in the section of the development method of the 3D printer model of the present invention of the present invention can be applied to this removal method. In that case, the development process in the development method of the 3D printer model, the first rinse The treatment step and the second rinsing treatment step correspond to step (1), step (2), and step (3) of the removal method, respectively, and preferable embodiments can be applied in the same manner.

  Further, the present invention is a 3D modeling method for modeling a three-dimensional object with a 3D printer, wherein the three-dimensional object modeled with a model material and a support material is processed with the developer composition for a 3D printer modeled object of the present invention. A 3D modeling method is also provided that includes the step of removing the support material. Of the matters described in the specification of the 3D printer modeled product development method of the present invention in this specification, all matters relating to the development step can be applied to the above-described steps in this method, and preferred aspects can be similarly applied. .

  The present invention also provides a developer kit for a 3D printer modeled article comprising the developer composition for a 3D printer modeled article of the present invention and an aqueous solution of an acid. The kit separates and holds the developer composition for a 3D printer modeled article of the present invention and an aqueous solution of an acid, and an article containing the developer composition for a 3D printer modeled article of the present invention; And an article containing an aqueous solution of an acid. In the present specification, all the matters described in the section of the developer composition of the present invention can be applied to this kit, and preferred embodiments are also the same. Further, in the present specification, among the matters described in the first rinsing process step of the present invention, all matters relating to the acid aqueous solution can be applied to this kit, and preferred embodiments are also the same.

[Test piece: 3D printer model]
Test piece 1: Using 3D printer Eden 350V manufactured by Objet Geometry, using FullCure 720 as the model material and FullCure 705 as the support material, Hao quality mode, stacking pitch 16μm, maximum long axis length A monkey wrench shaped article having a length of 112 mm, a short axis maximum length of 36 mm, and a maximum thickness of 7 mm was produced. This 3D printer is an inkjet ultraviolet curing method using an acrylic photo-curing resin, and both the model material and the support material are acrylic resins. An outline of the monkey wrench model is shown in FIG. In FIG. 1, the adjustable wrench portion is also shown by a solid line for convenience. The monkey wrench model has a variable opening width due to the worm gear, and has a groove and a screw hole.
Test piece 2: Using Dimension SST, a 3D printer manufactured by Stratasys, using P400 ABS MODEL as a model material and P400SR P400 Soluble Support as a support material, long axis length 112mm, short axis length 36mm, maximum thickness 7mm A monkey wrench model was prepared. This 3D printer is a hot melt lamination method using ABS resin, the model material is ABS resin, and the support material is thermoplastic acrylic resin. An outline of the monkey wrench model is shown in FIG. In FIG. 1, the adjustable wrench portion is also shown by a solid line for convenience. The monkey wrench model has a variable opening width due to the worm gear, and has a groove and a screw hole.

[Development test]
Various developer compositions having the compositions shown in Tables 1 and 2 were prepared, and the test pieces (monkey wrench shaped products) were developed using these developer compositions to develop the developer composition and model materials. The impact on was evaluated. In addition, all the developing solution compositions were colored blue by the reactive dye (kayashion), and in the examples, discoloration over time was observed in the developing solution composition during development.

(Development method)
The test piece 1 or the test piece 2 is used for 3 hours, 6 hours, or 12 hours at a liquid temperature of 25 ° C. so that the entire test piece is applied to the developer composition shown in Table 1 or Table 2. Immersion and development. Next, the test piece 1 or the test piece 2 after development is soaked in an acid aqueous solution containing the acid shown in Table 1 at the concentration shown in Table 1 (the balance being water), and the test piece 1 is immersed in the acid aqueous solution. The first rinse treatment was performed by dipping at 25 ° C. for 10 minutes. In some examples, the first rinsing process was not performed (displayed as “none” in the table). Next, the test piece 1 or the test piece 2 after the first rinsing treatment was rinsed with running tap water for 2 minutes to perform a second rinsing treatment. Subsequently, after air blowing for 1 minute, it was left to stand indoors for 1 hour and dried.

(Evaluation)
(1) Developability The removal state of the support material of each test piece after drying was visually observed. The observation was performed at three locations of the surface, groove, and screw hole, and the developability was evaluated according to the following criteria. Six panelists made the above observations for three test pieces, and the averages of the scores for the developability of the three test pieces are shown in Tables 1 and 2 as indices indicating the developability. In addition, it means that development performance is so favorable that the average value of the said score is large, and the support material is removed more favorably.
* Developability evaluation criteria: 5 points: The surface, grooves, and thread support holes are all removed, and the surface is smooth and smooth.
4 points: The support material on the surface, grooves, and screw holes are all removed, but the surface is slightly rough.
3 points: The support material on the surface, grooves, and screw holes are all removed, but there is roughness on the surface.
2 points: The support material on the surface and the groove is all removed, but the support material remains in the hole of the screw part.
1 point: All the support material on the surface has been removed, but the support material remains in the groove and the hole of the screw part.
0 point: The support material remains on the surface, the groove, and the hole of the screw part.

(2) Influence on model material The surface state of each test piece after drying was visually observed. Observation was performed on the surface of the test piece, and the influence on the model material was evaluated according to the following criteria. Each of the six panelists made the above observations for three test pieces. Tables 1 and 2 show the average of the above points regarding the influence on the surface of the three test pieces as indices indicating the influence on the model material. Indicated. In addition, it means that the influence on a model material is small and it is so favorable that the average value of the said score is large.
* Evaluation criteria for impact on model materials 3: No impact.
2: The surface was slightly dissolved.
1: Dissolved and reduced in size.

(A) component (part) and (d) component (part) in the table are as follows.
· POE (1) monobutyl ether: polyoxyethylene (average number of moles of ethylene oxide added 1) monobutyl ether · POE (2) monobutyl ether: polyoxyethylene (average number of moles of ethylene oxide added 2) monobutyl ether · POE (3) monomethyl Ether: polyoxyethylene (ethylene oxide average addition mole number 3) monomethyl ether / POE (8) monolauryl ether: polyoxyethylene lauryl ether, ethylene oxide average addition mole number 8
POE (20) monostearyl ether: polyoxyethylene stearyl ether, average added mole number of ethylene oxide 20
Alkenyl (C8) dipotassium succinate: carbon number of alkenyl group 8

  From the results of Tables 1 and 2, it can be seen that when the developer composition of the present invention is used, the support material is removed cleanly and high developability can be obtained. It can also be seen that when the developer composition of the present invention is used and the first rinsing treatment is performed with an aqueous acid solution, even higher developability can be obtained. The developer composition of the present invention has little influence on the model material, and it can be seen that a beautiful shaped product can be obtained. On the other hand, in a comparative example, it turns out that the effect of this invention is not acquired as follows.

Comparative Example 1: When the content of the alkali metal hydroxide of the component (b) is 0.3% by weight, the removability of the support material is reduced and swelling is performed, but most of the residue remains even after 12 hours of immersion. .
Comparative Example 2: When the content of the water-soluble organic solvent of the component (a) is 0.5% by weight, the permeability of the developer composition to the inside decreases, and the internal support material such as the hole of the screw portion Remained.
Comparative Example 3: When the (b) / (c) weight ratio was 1 / 0.25, the support agent removability decreased and the model agent was affected. That is, the contrast with the support agent was lowered and both were dissolved.
Comparative Example 4: When the content of the surfactant as the component (d) is 0.05% by weight, the rinsing properties of the developer composition and the support material dissolved in the developer composition are lowered, and there is a rinse residue on the surface. When the immersion time was short, the rinsability of the internal support material, such as the screw hole, was lowered.
Comparative Example 5: When the weight ratio of (b) / (c) was 1 / 0.2, the support agent removability decreased and the model agent was affected. That is, the contrast with the support agent is lowered, and both are dissolved. Compared with Example 4 that differs only in the (b) / (c) weight ratio, the decrease in performance is obvious.
Comparative Example 6: When the weight ratio of (b) / (c) was 1/5, the internal support material such as the hole of the screw portion could not be removed. This is presumably because the organic alkali agent inhibits the effects of saponification, decomposition, and collapse of the support material by the alkali metal hydroxide.
Comparative Example 7: When the weight ratio (b) / (c) was 1 / 0.3, the influence on the model material was significant.
Comparative Example 8: The support material could not be removed at all unless the alkali metal hydroxide of component (b) was contained.
Comparative Example 9: When the organic alkali agent of component (c) was not included, the influence on the model material was strong.
Comparative Example 10: When the water-soluble organic solvent of the component (a) was not contained, the permeability of the developer composition to the inside was lowered, and the internal support material such as a hole in the screw part could not be removed.
Comparative Example 11: When the surfactant of component (d) was not contained, the developer composition hardly penetrated into the inside of the threaded portion or the like, and the support material remained. In addition, the rinsing properties of the developer composition and the support material dissolved in the developer composition were lowered, and there was a rinse residue on the surface.
Comparative Example 12: When potassium carbonate is used instead of the component (b), the support material cannot be removed at all, and the developability is remarkably lowered. Compared with Example 8 which differs only in containing potassium carbonate instead of (b) component, the fall of performance is clear.
Comparative Example 13: Although it is the composition of Table 1 and Patent No. 2 of Patent Document 5 (Japanese Patent Application Laid-Open No. 2011-20412), it can be seen that the support material cannot be removed at all and the developability is extremely low.
Comparative example 14: Although it is a composition according to the patent document 4 (Unexamined-Japanese-Patent No. 2011-5658) Table 1, the solution 5, it turns out that a support material cannot be removed at all and developability is remarkably low.

Claims (11)

(A) water-soluble organic solvent 1 wt% or more, 20 wt% or less, (b) alkali metal hydroxide 0.5 wt% or more, 20 wt% or less, (c) organic alkali agent 0.2 wt% or more, 20% by weight or less, (d) 0.1% by weight or more of surfactant, 20% by weight or less, and water,
The content weight ratio of the content of (c) of (b) (b) / ( c) is 1/4 or more state, and are 1 / 0.4 or less,
As a support material, for a 3D printer model using a photocurable composition containing an acrylic monomer and a support material selected from a thermoplastic acrylic resin,
Developer composition for 3D printer shaped object. Furthermore, a colorant, according to claim 1 3D printer shaped article for developer composition. The development process of removing the support material by processing the 3D printer modeled object modeled with the model material and the support material with the developer composition for 3D printer modeled object, and the 3D printer modeled object after the development process with water or water A method for developing a 3D printer model, including a rinsing process for processing with a liquid containing
The developer composition for a 3D printer object is (a) a water-soluble organic solvent of 1% by weight to 20% by weight, (b) an alkali metal hydroxide of 0.5% by weight to 20% by weight, ( c) an organic alkali agent of 0.2 wt% or more and 20 wt% or less, (d) a surfactant of 0.1 wt% or more and 20 wt% or less, and water, and the content of (b) and (c the weight ratio of the content of) (b) / (c) is 1/4 or more, Ri 1 / 0.4 or less of the 3D printer shaped object for developer composition der,
The support material consists of a support material selected from a photocurable composition containing an acrylic monomer and a thermoplastic acrylic resin.
Development method of 3D printer model. Rinsing process is
A first rinsing process for treating the 3D printer model after the development process with an aqueous solution of an acid, and a second rinsing process for treating the 3D printer model after the first rinsing process with water,
The development method of 3D printer modeling thing of Claim 3 containing this. The method for developing a 3D printer model according to claim 4 , wherein the first rinsing process is performed by immersing the 3D printer model in an aqueous acid solution. 3D printer, a 3D printer that uses a movable nozzle with built-in jet nozzle or heater, the developing method of the 3D printer shaped article according to any one of claims 3-5. The model material is made of an ultraviolet curable composition, and the temperature of the developer composition for a 3D printer shaped article used in the development step is 5 ° C or higher and 40 ° C or lower, according to any one of claims 3 to 6 . Development method of 3D printer model. The method for developing a 3D printer model according to any one of claims 3 to 7 , wherein the development step is performed by immersing the 3D printer model in a developer composition for a 3D printer model. The method for developing a 3D printer model according to any one of claims 3 to 8 , wherein the developer composition for a 3D printer model is colored. 3D building process to produce a 3 D printer shaped article consisting of a model material and support material with a 3D printer,
A development process for removing the support material from the 3D printer model by processing the 3D printer model obtained in the 3D model process with a developer composition for a 3D printer model;
A method for manufacturing a 3D printer model including a rinsing process for processing the 3D printer model after the development process with water or a liquid containing water,
The developer composition for a 3D printer object is (a) a water-soluble organic solvent of 1% by weight to 20% by weight, (b) an alkali metal hydroxide of 0.5% by weight to 20% by weight, ( c) an organic alkali agent of 0.2 wt% or more and 20 wt% or less, (d) a surfactant of 0.1 wt% or more and 20 wt% or less, and water, and the content of (b) and (c the weight ratio of the content of) (b) / (c) is 1/4 or more, Ri 1 / 0.4 or less of the 3D printer shaped object for developer composition der,
The support material consists of a support material selected from a photocurable composition containing an acrylic monomer and a thermoplastic acrylic resin.
Manufacturing method of 3D printer modeling thing. Rinsing process is
A first rinsing process for treating the 3D printer model after the development process with an aqueous solution of an acid; and a second rinsing process for treating the 3D printer model in the first rinsing process with water.
The manufacturing method of 3D printer modeling thing of Claim 10 containing these.

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